Any natural geologic hydrocarbon formations that have porosity and permeability that allow hydrocarbons to migrate are target locations for this invention. A fuel cell technology is applied to electrochemically separate nitrogen from air and then pressurize nitrogen diamers and nitrogen compounds through hydrocarbon formations. Where nitrogen compounds violently react with hydrocarbons, a large number of SCF nucleation sites are formed from the instant compression of nitrogen diamers (N2) into supercritical nitrogen (scN2).
SCF cells form when hydrocarbon-reactants violently react (micro-bursts of energy) with hydrocarbons, because gas molecules travel only short distances in straight lines before they are deflected in a new direction by collision with other gas molecules that are further confined inside the small pores (in geology a small space that is surrounded by rock or soil and filled with hydrocarbon gases, fluids and solids) of natural hydrocarbon formation rock and soil that includes fluid and solid fills. The gas velocity formula below can be applied under the kinetic-molecular theory of gases to explain why open gas permeable formations that have very small or low porosity can still have gas and liquids phase into instances of SCF cells. Prior SCF art does not teach that open porous geologic formations can provide the environment for a SCF event to move hydrocarbons out of the formation. SCF oil and gas recovery focuses on breaking down the hydrocarbons for movement, by minimizing or limiting chemical reactions to SCF formation.
The kinetic-molecular theory (KMT) of gases can be stated as four postulates:
1. A gas consists of molecules in constant random motion.
2. Gas molecules influence each other only by collision; they exert no other forces on each other.
3. All collisions between gas molecules are perfectly elastic; all kinetic energy is conserved.
4. The volume actually occupied by the molecules of a gas is negligibly small; the vast majority of the volume of the gas is empty space through which the gas molecules are moving.
Gas Velocity Explained
The root mean square velocity of a molecule can be obtained by using the formulavrms=(3RT/M)1/2 
Example: Calculate the root-mean-square velocity of oxygen molecules at room temperature, 25° C. M is the molecular mass of oxygen which is 31.9998 g/mol; the molar gas constant is 8.314 J/mol K, and the temperature is 298.15 K. The molecular mass must be divided by 1000 to convert it into a usable form, thereforevrms=(3(8.314)(298.15)/(0.0319998))1/2=481.2 m/s
So an oxygen molecule travels through the air at 481.2 m/s which is 1726 km/h, much faster than a jetliner can fly and faster than that of most rifle bullets.
The very high speed of gas molecules under normal room conditions would indicate that a gas molecule would travel across a room almost instantly. In fact, gas molecules do not do so. If a small sample of a very odorous (and poisonous) gas, H2S is released in one corner of a room, our noses will not detect it in another corner of the room for several minutes unless the air is vigorously stirred by a mechanical fan. The slow diffusion of gas molecules which are moving very quickly occurs because the gas molecules travel only short distances in straight lines before they are deflected in a new direction by collision with other gas molecules.
The distance any single molecule travels between collisions will vary from very short to very long distances, but the average distance that a molecule travels between collisions in a gas can be calculated. This distance is called the mean free path of the gas molecules. If the root-mean-square velocity is divided by the mean free path of the gas molecules, the result will be the number of collisions one molecule undergoes per second. This number is called the collision frequency of the gas molecules.
The postulates of the KMT of gases permit the calculation of the mean free path of gas molecules. The gas molecules are visualized as small hard spheres. Without going into the mathematical detail; as the temperature raises the mean free path increases; it also rises as the pressure decreases, and as the size of the molecules decrease. Taking all this into account, the oxygen molecules from above has a mean free path of 67 nm. Diffusion takes place slowly because even though molecules are moving very fast, they travel only short distances in any one straight line.
This invention teaches that a propellant is a material used to move an object by applying a motive force provided after a SCF penetration into hydrocarbons. This may or may not involve a chemical reaction. It may be a gas, liquid, plasma, or, before the chemical reaction, a solid. As some gas escapes to expel the hydrocarbons in a formation, more new SCF forms back pressure as liquid evaporates into new gas, maintaining a motive force of pressure. Pressure acts in all directions at a point inside a gas. At the surface of a gas, the pressure force acts perpendicular to the surface forcing gases, liquids, and solids out of the formation.
This invention teaches spontaneous reactions (in opposition to non-spontaneous reactions) do not need external perturbations (such as energy supplement at the oil well borehole) to happen at a great distance from the infusion of reactants at borehole. An irreversible reaction is one in which nearly all of the reactants (minor gas) are used to form products. These reactions are very difficult to reverse even under extreme conditions. Although all reactions are reversible to some extent, this invention focuses on reactions that can be classified as irreversible. A reaction is called spontaneous if it thermodynamically causes a net increase on global entropy. In a hydrocarbon bearing formation at chemical equilibrium, it is expected to have larger concentrations of the substances formed from SCF forming back pressure as liquid evaporates into new gas in the spontaneous direction of the reaction, maintaining a motive force of pressure away from the reactant source borehole. Every chemical reaction is, in theory, reversible. In a forward reaction the substances defined as reactants are converted to products. In a reverse reaction products are converted into reactants. Chemical equilibrium is the state in which the forward and reverse reaction rates are equal, thus preserving the amount of reactants and products. A reaction in equilibrium can be driven in the forward or reverse direction by changing reaction conditions such as temperature or pressure elevated by SCF formation. Le Chatelier's principle can be used to predict whether products or reactants will be formed from reactions that form SCFs.
Le Chatelier's Principle can be summarized: When a chemical system at equilibrium experiences a change in concentration, temperature or total pressure the equilibrium will shift in order to minimize that change. The principle is used by chemists in order to manipulate the outcomes of reversible reactions, often to increase the yield of reactions.
Concentration of an ingredient will shift the equilibrium to the side that would reduce that change in concentration. This can be illustrated by the equilibrium of carbon monoxide and hydrogen gas, reacting to form methanol.CO+2H2CH3OH
Suppose we were to increase the concentration of CO in the system. Using Le Chatelier's principle we can predict that the amount of methanol will increase, decreasing the total change in CO.
Temperature: Let us take for example the reaction of nitrogen gas with hydrogen gas. This is a reversible reaction, in which the two gases react to form ammonia:N2+3H22NH3ΔH=−92 kJ/mol
This is an exothermic reaction when producing ammonia. If we were to lower the temperature, the equilibrium would shift in such a way as to produce heat. Since this reaction is exothermic to the right, it would favour the production of more ammonia. This reaction is used in the Haber process, which is a good example of the way chemists use Le Chatelier's principle.
In a Total Pressure manipulation we can refer to the reaction of nitrogen gas with hydrogen gas to form ammonia:N2+3H22NH3ΔH=−92 kJ/mol
Note the number of moles of gas on the left hand side, and the number of moles of gas on the RHS. We know that gases at the same temperature and pressure will occupy the same volume. We can use this fact to predict the change in equilibrium that will occur if we were to change the total pressure.
Suppose we increase total pressure on the system, now by Le Chatelier's principle the equilibrium would move to decrease the pressure. Noting that 4 moles of gas occupy more volume than 2 moles of gas, we can deduce that the reaction will move to the right if we were to increase the pressure.
Nitrous oxide (N2O), ammonia (NH3), and hydrazine (N2H4) are nitrogen compounds that are target gas and violently react with hydrocarbons. Nitrous oxide or ammonia or hydrazine or nitric acid (HNO3) compounds will react with hydrocarbons. Ammonia and hydrazine react explosively with petroleum.
Nitrogen tetroxide (or dinitrogen tetroxide) (N2O4) is a hypergolic propellant often used in combination with a hydrazine-based rocket fuel. The combination was used to fuel the Titan rockets used in the Gemini missions, and it is still used today in the second stage engines of Delta II rockets. By the late 1950s, it became the storable oxidizer of choice for rockets in both the USA and USSR.
Nitrogen dioxide is made by the catalytic oxidation of ammonia: steam is used as a diluent to reduce the combustion temperature. Most of the water is condensed out, and the gases are further cooled; the nitric oxide that was produced is oxidized to nitrogen dioxide, and the remainder of the water is removed as nitric acid. The gas is essentially pure nitrogen tetroxide, which is condensed in a brine-cooled liquefier.
Nitrogen tetroxide is a liquid that is easily vaporized. It is a powerful oxidizer and is highly toxic and corrosive. It is not affected by mechanical shock and does not react with air. Nitrogen tetroxide is always in equilibrium with nitrogen dioxide (NO2), and some nitrogen dioxide will be present in any quantity of nitrogen tetroxide (higher temperatures push the equilibrium towards nitrogen dioxide). Nitrogen tetroxide reacts with water to form nitric acid.
Reactions of Nitric Acid
Dinitrogen pentoxide, N2O5, is best prepared by dehydrating concentrated nitric acid, HNO3, by phosphorus pentoxide, P2O5.2HNO3+P2O5N2O5+2HPO3 
Nitric oxide, NO, is prepared by the action of copper, Cu, or mercury, Hg, on dilute nitric acid, HNO3, and was called nitrous air.3Cu+8HNO33Cu(NO3)2+2NO+4H2O
Nitrogen dioxide, NO2, is a mixed acid anhydride and reacts with water to give a mixture of nitrous and nitric acids.2NO2+H2HNO2+HNO3 
If the solution is heated, the nitrous acid decomposes to give nitric acid and nitric oxide.3HNO2HNO3+2NO+H2O
Sulphur dioxide, SO2, and nitrogen oxides, NOx, are toxic acidic gases, which readily react with the water in the atmosphere to form a mixture of sulphuric acid, nitric acid, and nitrous acid as acid rain.
Nitrates are the salts of nitric acid and are strong oxidizing agents.
The Oswald Process is the three-stage process by which nitric acid is manufactured. First, ammonia, NH3, is oxidized at a high temperature (900° C.) over a platinum-rhodium catalyst to form nitrogen monoxide, NO.4NH3 (g)+5O2 (g)4NO (g)+6H2O
The nitrogen monoxide, NO, cools and reacts with oxygen, O2, to produce nitrogen dioxide, NO2.2NO (g)+O22NO2 (g)
Finally, the nitrogen dioxide, NO2, reacts with water and oxygen, O2, to produce nitric acid,4NO2 (g)+2H2O (l)+O24HNO3 (l)
All oxides of nitrogen are polar covalent compounds. The lower oxides of nitrogen are neutral oxides. The higher oxides of nitrogen are acidic oxides. The oxides of nitrogen are formed during high temperature combustion, and are present in exhaust gases from these processes. The principal oxides of nitrogen, NOx, are nitrous oxide, nitric oxide, nitrogen dioxide, nitrogen pentoxide, and dinitrogen tetroxide. Combustion emissions are typically optimized to reduce NOx. This invention teaches that high temperature combustion processes can be modified to produce higher volumes of oxides of nitrogen that are reactive with hydrocarbon, under pressure of exhaust, and can be infused into hydrocarbon formations to form SCF and propulsion of hydrocarbons out of the formation. A combustion engine, fuel cell, or turbine can be modified to optimize the production of combustion NOx emissions to a volume high enough to reinject into a geologic formation. Piston, combustion chamber, fuel to air mixtures, exhaust, intake, and pollution controls can be removed to accomplish this gas supply in an engine. Turbine intake, exhaust, fuel to air mixtures, turbine speed, operating temperatures, and pressures can be reduced in efficiency to produce high NOx emission for injection into oil formations. An alternative to fuel cells, Air Liquide of Houston Tex. USA provides FLOXAL™ solutions (FLOXAL™ Nitrogen, FLOXAL™ Oxygen, FLOXAL™ Hydrogen and FLOXAL™ Air), which are adapted in real time to production volume requirements, paying attention to continuity of supply.
A general solubility property of gases (a behavior described by Graham's Law and by Dalton's Law of Partial Pressures) is that they diffuse to fill the volume in which they are contained. Gases have neither fixed shape nor fixed volume; therefore, gases that do not react with each other are infinitely soluble in each other in all proportions due to this power of diffusion. SCF form from gas species and progress to combine with liquids that are in an SCF state, forming one solution that penetrates hydrocarbon solids at nearly 100 percent, moving the hydrocarbons with the greatest efficiency.
A gas that dissolves in a liquid with which it does not react is uniformly distributed throughout the volume of the solvent, and its behavior is described by Henry's Law. Generally, the solubility of a gas that is only slightly soluble in a solvent decreases with increasing temperature. Hydrogen, nitrogen and oxygen are non-polar and are only slightly soluble in water. In the case of these three gases, the gases continue to exist as covalent molecules in solution and there is no significant alteration to the structure of the molecules of gas. Hydrogen and nitrogen make the ideal SCFs because of this behavior.
A polar covalent gas that dissolves in a polar solvent often undergoes chemical reaction with the solvent, and significant changes to the structure of the molecules of the gas occur in solution (e.g. the polar covalent gas ammonia is very soluble in water and in aqueous solution, ammonia exists as an ammonium ion, NH4(+), having extracted a hydrogen ion from a molecule of water). Ammonia, NH3+H2ammonium ion NH4(+)+hydroxyl ion HO(−). The resulting solution is alkaline due to the existence of the hydroxyl ion in solution.
Hydrocarbon reactants other than nitrogen compounds are taught in this invention. Hydroxyl radicals act like a detergent (and can be carried in suspension as a neutral solution), reacting with carbon monoxide, methane, and other hydrocarbons and so oxidizing them to form scWater and scCarbon dioxide miscible SCFs in situ. Hydroxyl radicals reactions move hydrocarbons out of formation, and are significant replacements for other gases (or liquids) when there is too much water for anhydrous ammonia to adsorb. Alternative SCF reactions are important, because nature is not the same for each geologic formation. Water alone can be removed from the ground from the infusion of hydroxyl radicals.
Hydroxide is a polyatomic ion consisting of oxygen and hydrogen:—O—H
It has a charge of −1. Hydroxide is one of the simplest of the polyatomic ions. The term hydroxyl group is used to describe the functional group —OH when it is a substituent in an organic compound. Organic molecules containing a hydroxyl group are known as alcohols (the simplest of which have the formula CnH2n+1-OH). A group of bases containing hydroxide are called hydroxide bases. Hydroxide bases will dissociate into a cation and one or more hydroxide ions in water, making the solution basic. Hydrogen hydroxide is another name for water, as is hydrohydroxic acid. Both names are based on the hydroxide ion. The hydroxyl radical, OH, is the neutral form of the hydroxide ion. Hydroxyl radicals are highly reactive and consequently short lived. Most notably, hydroxyl radicals are produced from the decomposition of hydro-peroxides (ROOH).
This invention focuses on providing the process of SCF only when hydrocarbons are present, which offers a wide range of solvent power at a great distance from the source, chemical selectivity, environmental control, economics, and safety. This invention uses SCFs as an environmentally acceptable alternative to conventional solvents for reaction chemistry in hydrocarbon oil and gas recovery.
This invention teaches environmental control and safety by selecting reaction compound species for their entropy, enthalpy, and economy in volumes that react violently under the critical point in open spaces of the formation and above the critical point, forming SCF when the same reaction occurs in substantially higher density formations where the concentration, temperature, and pressure can produce a motive pressure. In many cases, the porosity, or open cavity, will be so great in volume that a SCF potential fluid will not form from a violent reaction, because the reaction zone cannot build pressure and temperature rapidly enough to move above the critical point. The violent reaction still develops pressure to move hydrocarbons out of a formation and is under the spirit of this invention where the reaction simply becomes a propellant to move hydrocarbons. This invention teaches an SCF forms from violent reaction (micro-bursts of energy) with hydrocarbons within the confinement of high-density porous hydrocarbon formations in which the substance at a temperature and pressure rises instantaneously above its thermodynamic critical point, penetrating and moving the hydrocarbons from the solvent penetrating energy power of an SCF. In nature there is an infinitely variable set of formation sizes, depths, porosities, formation materials, hydrocarbon mixtures, and quantities of each.
An SCF is any substance at a temperature and pressure above its thermodynamic critical point (FIG. 14). SCFs have the unique ability to diffuse solids, like a gas, and dissolve materials into their components, like a liquid. Furthermore, SCFs can readily change in density above the critical point and still remain in a supercritical state. Rapid expansion of supercritical solutions can lead to precipitation of a finely divided solid. SCF extraction is a process with properties that make SCFs suitable as a substitute for organic solvents. Carbon dioxide (CO2) and water are commonly used as SCFs for this purpose. Supercritical scCO2 (Tc=31.1° C., Pc=73.8 bar) closely resembles n-hexane in its solvating power, which can be further tuned by the addition of modifiers (including co-solvents and phase transfer catalysts) to afford the solubility characteristics required by the reaction selected for. Water's critical point occurs at around Tc=647 K (374° C. or 705° F.) and Pc=22.064 MPa (3200 PSIA), providing scH2O. SCF is defined by the critical temperature and pressure of any substance. SCFs have solvent power similar to a light hydrocarbon for most solutes. Fluorinated compounds are often more soluble in scCO2 than in hydrocarbons. Solubility increases with increasing density, which is provided from increasing pressure. Fuel cells require gases that are broken down from their original complex hydrocarbon to process the simple gas across the fuel cell membranes, and these complex hydrocarbons are broken down in situ by SCF's migration within the hydrocarbon formation.
Fluids such as supercritical xenon, ethane, and carbon dioxide offer a range of unusual chemical possibilities in both synthetic and analytical chemistry. Supercritical carbon dioxide is the most widely studied. Others include nitrogen, propane, propene, butane, xenon, ethane, and water. The effect is similar to a normalizing constant. The fluids are completely miscible with permanent gases (e.g. N2 or H2), and this leads to much higher concentrations of dissolved gases than can be achieved in conventional solvents. This effect is applied in both organometallic reactions and hydrogenation.
SCF modifier solvents: Small amounts of a second solvent can be added to the SCF. This can result in a change in solvent polarity and nature, which follows Snyder rules. This requires a proton donor (1-2-propanol), proton acceptor (2-acetonitrile), and dipole (3-dichloromethane). Synthetic organic chemists, inorganic chemists, physical chemists, and chemical physicists who employ a synergic blend of experimental, theoretical, and computational techniques can identify target compounds, attempt their synthesis on a laboratory scale, characterize new materials, and perform larger-scale synthesis of promising new species for formulation and application as SCFs to remove hydrocarbons from geologic formations. SCFs can be combined in any number of materials and can be synthetic or natural material combinations that will penetrate the hydrocarbon-bearing formation. Natural gases and decomposed hydrocarbons from hydrocarbon-bearing formations can be phased into SCFs as part of the supercritical process of extraction.
Robert Frisbee of Jet Propulsion Laboratory (JPL) researched ways of incorporating a little monatomic hydrogen into anything with even a little stability for application in ultra-high performance propulsion for planetary spacecraft. A selected list of propellants (adapted from Frisbee, 1983) demonstrates: solids (IUS(3) â‰^3.0 m/s), monopropellants, bipropellants, and tripropellants, free radicals (unstable), and nuclear thermal (â‰^3500K). These propellants are man-made for rocket propulsion; in contrast, oil recovery is natural and will have many more gas species grouped together in excess of tripropellants as part of SCFs and propellants. The high number of natural gas species in the infinitely variable hydrocarbon-bearing formations and the conversion of many of these gases into propellants above tripropellants is part of the teaching of this invention. The following is a list of organic and inorganic propellants that can be produced from SCF inside hydrocarbon formations to move them out of the formation. These propellant compounds with such positive enthalpies are explosive in situ when combined. Some of the propellants are too large and explosive to apply (10CH2+72NH4ClO4+18Al) in situ and others are small enough and have a low enough enthalpy to move into the formation porosity to form SCF within the formation permeability. Pure fluorine (F2) is a corrosive pale yellow gas that is a powerful oxidizing agent. It is the most reactive and electronegative of all the elements and readily forms compounds with most other elements. Fluorine even combines with the noble gases, krypton, xenon, and radon. Even in dark, cool conditions, fluorine reacts explosively with hydrogen. In a jet of fluorine gas, glass, metals, water and other substances burn with a bright flame. It is far too reactive to be found in elemental form and has such an affinity for most elements, including silicon, that it can neither be prepared nor should be kept in glass vessels. In moist air, it reacts with water to form the equally dangerous hydrofluoric acid. F2 is not a good selection for infusion into hydrocarbon formations.
PROPELLANT SPECIFIC IMPULSE m/s Ideal (I) Field (F) “Field” refers to actual engine firing data.
Solids: (IUS(3) â‰{circumflex over ( )} 3.0 m/s)10CH2 + 72NH4ClO4 + 18AlI = (4)F = 3.3310CH2 + 52NH4ClO4 + 20AlI = (4)F = 3.4014CH2 + 72NH4ClO4 + 14BeI = (4)F = 3.40MonopropellantsH2O2 (hydrogen peroxide)I = 2.40F = 1.88N2H4 (hydrazine)I = 2.64F = 2.59BipropellantsClF5 + N2H4I = 3.79F = 3.65N2O4 + N2H4 (5)I = 3.96F = 3.47O2 + RP-1 (6)I = 4.52F = 3.73O2 + H2 (SSME)I = 4.97F = 4.61F2 + N2H4I = (4)F = 4.28F2 + H2I = 5.18F = 4.91TripropellantsF2 + H2 + Li(7)I = 6.89F = (4)O2 + H2 + Be(7)I = 6.91F = (4)Free Radicals (Unstable)O3 + H2I = 5.95F = 5.01H + HI = 20.89F = (4)Nuclear Thermal (â‰{circumflex over ( )}3500 K)CH4I = 6.00F = (4)H2I = 11.00F = (4)
(1) All chemical energy converted to kinetic energy
(2) Modeled for optimum expansion from 6894 kP to 1.379 kP (1000 psia to 0.2 psia, 0.014 atmosphere)
(3) Inertial upper stage—a solid fuel upper stage
(4) No data provided
(5) Ignites on contact. Typical of Titan main engines
(6) Typical of Atlas and Delta main engine
(Reference: Frisbee, Robert, “Ultra High Performance Propulsion for Planetary Spacecraft,” JPL D-1184, Pasadena, Calif., 1983)
Processing conditions provide the pressure and temperature necessary to control hydrocarbon-bearing formation penetration of SCFs. Nitrogen in the elemental form was considered to be inert and was even named ozote, which refers to the fact that it is not reactive. Of course nitrogen does form compounds, but the gaseous form consists of diamers N2 (2 nitrogen molecules bonded together). The nitrogen diamer is very stable, and three nitrogen molecules (N3) are also relatively stable.
Nitrogen is a major element in organic compounds. Some nitrogen compounds are highly reactive. Trinitrotoluene is TNT or dynamite. Ammonium nitrate is a fertilizer, but was used as the major explosive ingredient in the Oklahoma City bombing. Anfo, or ammonium nitrate and fuel oil mixture, is the primary explosive used in the mining industry because it is inexpensive, easy to manufacture, and can be easily manufactured near the mine site, thus reducing the risks and expenses related to the transportation of explosives: nitrates, nitrites, and azides (all nitrogen compounds are either oxidizers or reactives and will react violently under the right conditions). There are 221 known nitrogen compounds to select from, depending on hydrocarbon-bearing formation materials and the ability to form a compound in the fuel cell or fuel cell housing. This invention is not limited to nitrogen compounds such as the hydrocarbon-reactive materials. Any compound that is reactive when exposed to hydrocarbons can be injected through the oil or gas bore hole by providing a supply line of compressed gases from above ground and still be within the spirit of this invention. Several bore holes can be provided to supply multiple potential SCFs through each bore hole, or SCFs can be formed from the combination of the violent reactions between non-hydrocarbon materials. It is an objective of this invention to penetrate the full volume of the hydrocarbon formation (e.g. propane migrates to the lowest points in the geologic formation and hydrogen migrates to the highest points in the formation, providing full coverage of potential compressible SCFs). As SCFs penetrate the hydrocarbon formation and migrate out hydrocarbons, many of the natural gases, such as carbon dioxide, nitrogen, hydrogen, propane, and methane, will be compressed into SCFs. The most economic method of SCF formation is supplying a single hydrocarbon reactive compound into the hydrocarbon-bearing formation at a level at which when it contacts hydrocarbon, it will violently react, compressing the natural gases, fluids, and materials into the SCF state, penetrating the hydrocarbons for migration out of the formation.
Non-solid fuels include oil and gas (both fuel types have various varieties). Crude oil consists of a mixture of petroleum liquids and gases (together with associated impurities) pumped out of the ground through oil wells. Oil is a generic term for fluids that are not miscible with water. In the United States, petroleum is referred to predominantly as oil. Petroleum (from Latin petrus, rock, and oleum, oil) or mineral oil is a thick, dark brown or greenish flammable liquid, which, at certain points, exists in the upper strata of Earth's crust. It consists of a complex mixture of various hydrocarbons, largely of the methane series, but may vary much in appearance, composition, and properties. Natural gas, which is about 80% methane, with varying proportions of ethane, propane and butane, is used as a fuel.
Coal is a solid fossil fuel extracted from the ground by mining. It is a readily combustible black or brownish-black rock. It is composed primarily of carbon and hydrocarbons, along with assorted other elements, including sulfur.
All these types of fuel are combustible: they create fire and heat.
A fuel cell is not needed in this invention to practice the art of SCF penetration into hydrocarbon formations. This invention teaches the infusion of hydrocarbon-reactive compounds into hydrocarbon-bearing formations that violently react (micro-bursts of energy) with hydrocarbons compressing gases (supplied from above ground, a fuel cell, or naturally within the formation) into SCF with nearly 100 percent penetration into hydrocarbons for extraction. The potential SCF or as may be natural to the formation and may be any material, including any number of reactants or any number of SCFs combined to migrate hydrocarbons out of the formation. This invention teaches that water may be removed from a geologic formation by selecting for it. This invention teaches that the SCFs can be selected for and combined, if needed, to penetrate the upper or lower regions of the formation. Water adsorbs anhydrous ammonia and can be saturated with anhydrous ammonia (e.g. 25% adsorption), which will react with hydrocarbons when injected into a geologic hydrocarbon formation, forming sCH2O (supercritical water). sCH2O has its own unique behavior just prior to going supercritical, because the water dissolves into the formation and is adsorbed, releasing the anhydrous ammonia at the most opportune time. Waste steam from a solid oxide fuel cell can have the anhydrous ammonia added to it as the steam is introduced to the hydrocarbon formation.
Infusion of fuel cell produced nitrogen diamers in hydrocarbon-bearing formations where very stable major-gas nitrogen diamers (2 nitrogen bonded together with traces of 3 nitrogen) do not react with hydrocarbons. When combined with minor-gas nitrogen compounds that are highly reactive (nitrates, nitrites and azides) and with hydrocarbons, they react as a fast, thorough hydrocarbon migration technique to enhance oil recovery in oil fields, completely recovering additional reserves or prolonging production after primary, secondary, and tertiary recovery methods no longer produce oil or gas economically.
SCF increases production efficiency of older fields that can be prolonged by in-situ fuel cell refining of hydrocarbons from within hydrocarbon-bearing formations. The major gas being infused is very stable nitrogen diamers combined with minor gas highly reactive nitrogen compounds: nitrates, nitrites and azides (all nitrogen compounds are either oxidizers or reactives and will react violently under the right conditions). When the minor highly reactive nitrogen compounds (nitrates, nitrites and azides) reach hydrocarbon in formations, even at great distances, a micro-violent reaction occurs, compressing stable nitrogen diamers into an SCF with the rapid dissolution rate required to penetrate hydrocarbon-bearing formations as an SCF solvent. This invention teaches that SCF energy can be injected into hydrocarbon-bearing formations when minor traces of highly reactive nitrogen gas compounds reach hydrocarbons; they react violently, compressing the major gas, nitrogen diamers, into the SCF state of scN2 within hydrocarbon cells (natural geologic hydrocarbon formations within the non-hydrocarbon micro-porosity), forming a large number of nucleation sites (orders of magnitude more hydrocarbon penetration by SCFs than would naturally form from nitrogen diamers migration alone) where controlled cell growth occurs. A large and rapid pressure drop immediately follows SCF states to create the large number of uniform migration sites. Cells are expanded by diffusion of gas into bubbles (phasing out of their SCF energy state) containing both hydrocarbons and stable nitrogen diamers, further migrating hydrocarbons from the hydrocarbon-bearing formation.
A fuel cell generates electricity from continuously supplied streams of fuel and oxidant. The two streams do not mix or burn, but produce electricity by electrochemical reactions similar to a conventional battery. The details of the chemical reactions depend on the type of fuel cell, but in all types an electrically charged ion is transferred through an electrolyte, which physically separates the fuel and oxidant streams. The fuel cell thus provides an elegant means of converting the chemical energy of the fuel directly into electrical energy.
Fuel cell assemblies are inserted down hole into a hydrocarbon-bearing formation, regulated by above ground oxygen air supplies down hole, and only upper lightweight environmentally safe atmospheric air is regulating working gas down hole. Waste gas and steam of the fuel cell are infused into hydrocarbon formations between the bore hole inner diameter wall and the plurality of infinitely variable seals that seal the fuel cell assembly within the bore hole. Coal, tar sands, petroleum-contaminated soil, shale beds, and/or oil wells that have lost gas pressure can also have hydrocarbon recovery by this invention's in-situ method.
Gas-refining in situ is provided by a plurality of bore hole seals separating and migrating the fuel cell gases into hydrocarbon formations. This invention teaches an oil well recovery system to target the release of nitrogen in the lower formations and steam in the upper formations, which result from down hole fuel cells that release steam and nitrogen. This decomposes the formation, increasing the pressure in the formation with a violently reacting propellant fuel relative to hydrocarbons pushing out hydrocarbons and water. This multi-sealed fuel cell heat exchanger and conduit vessel can be inserted down hole within any hydrocarbon-bearing formation: shale bed, oil formation, gas formation, water membrane, coal, contaminated ground, and tar sands, to provide migration of hydrocarbons from hydrocarbon-bearing formations, consuming the decomposed organics as fuel cell fuels.
Changing the lengths of the intake and exhaust tubes, seal locations and manifolding separates the system components, positioning them within hydrocarbon-bearing formation locations, possibly multiple systems applied to multiple formations within one bore hole.
A plurality of down hole gas seals are applied at variable depths to isolate and separate gas in the gradient of gases desorbed from hydrocarbons; the lighter gases are at the top and larger gas molecules are at the bottom of the bore hole. In addition to gas separation, a plurality of down hole gas seals provides a higher gas pressure, which is required at the inlet fuel-port of fuel cells to prevent parasitic energy loss of 4.4 to 7.5 kW/hr's from fuel compressors required in the absence of pressurized fuel. This down hole gas separation with a plurality of seals is gas refining in situ.
By separating the gases between multiple seals down hole, a blend of all the gases can be delivered to the fuel cell at 3 to 5 atmospheres of pressure. Hydrogen is a major component of sour gas, and this invention teaches that fuel cells can consume the majority of hydrogen to make water, electricity, and heat in the range of 1200° F. to 1800° F. needed for further hydrocarbon migration. This invention teaches controlling the gas separation down hole by the placement of a plurality of seals regulated through a manifold that separates gases for blending in the fuel cell, which provides the production of nitrogen diamers and nitrogen compounds. The fuel cell computer control is wired to sensors throughout the fuel cell for programming precise temperatures and pressures for optimized electrochemical reactions. An elevated temperature of 250° F. to 1240° F. fuel cell exhaust temperature is desirable as a source of heated gas passing through the down hole heat exchanger. This invention teaches production of fuel exhaust gases and post-processing fuel cell exhaust gases at a range of 250° F. to 1800° F., moving the gases (e.g. steam and nitrogen) into the porous hydrocarbon-bearing formation gases, liquids, and solids, providing continuous pressure to move hydrocarbons out and infusion of stable nitrogen diamers (N2) combined with traces of hydrocarbon-reactive nitrogen compounds into hydrocarbon-bearing formations.
An ideal location for low-pressure oil recovery is where limestone cap formations exist above the hydrocarbon formations, because in these cases a fuel cell in situ below the limestone and within fluid communication of the hydrocarbon formation can produce water steam pressure and approximately 78% nitrogen waste gas for injection into the formation. Nitrogen diamers infusion into the formation is preferred over steam, because the nitrogen is relatively inert and does not react with the hydrocarbons or the formations that the hydrocarbons are held in. Steam from the fuel cell in contrast can be applied to pressure some formation where the porosity, permeability, and formation materials will tolerate the water and steam pressures. In prior steam injection art, hydrocarbon formations collapse from water-dissolving formations. This invention teaches a down hole fuel cell that converts intake air from above ground and hydrocarbons from within the formation to produce nitrogen and steam that can be infused into the formation, adding pressure in hydrocarbon formations that have porosity and permeability. This allows hydrocarbons to migrate to nearby bore holes in fluid communication with the same formation. Core sample records could determine if the formation can tolerate the addition of steam; nitrogen is always going to be the preferred gas to increase hydrocarbon formation pressure for hydrocarbon migration.
FuelCell Energy, Inc. or Rolls-Royce Fuel Cell systems are more durable and maintainable than the nearest competitors. The Rolls-Royce Fuel Cell is produced by screen printing on low-cost ceramic type materials using proven production processes and minimal exotic materials. Hybrid fuel cells can easily be made by screen printing other chemical compounds onto the ceramics; another electrolyte, a catalyst for producing nitrogen compounds, etc. . . . . Profile, size, and weight make solid oxide fuel cells (SOFCs) suitable for distributed generation with potential for power densities equivalent to gas turbine systems. SOFCs have negligible air emissions (i.e. SOx, NOx, CO, and particulate matter), minimal noise profile, and can be entirely recycled at the end of its useful life. Unique modular SOFC designs can enable field change-out without interruption of supply and enhance support through state-of-the-art diagnostic and prognostic systems. Safety in operation is realized because the Rolls-Royce SOFCs system contains less than ten seconds of fuel supply at any time. Durability, low parts count, and the elimination of low durability components gives a realistic design target of 40,000 hours of operation on a mature product and a 20-year, 160,000-hour overall plant life potential. SOFC systems can be configured to use existing hydrocarbon-based fuels, i.e. natural gas and liquid fuels, and alternative fuels such as coal gas and bio-mass.
Because fluid and gas molecules can move around quickly, temperature differences do not build up in fluids or gases. Convection is the process that distributes the hot gases evenly in a heated hydrocarbon formation. If a mechanical means is used to increase convection, for example, a pump (or compressor) or fan, the process is called forced convection. Forced convection is an option used in this invention to heat the hydrocarbon formation when natural convection no longer yields a gas: a compressor circulates working gases continuously along the fuel cell to carry away excess heat. Conduction processes may occur in the liquids and gases, but for these fluids, it is difficult to prevent motion of parts of the gases and liquids; once molecules are in motion transporting heat, they are converted to circulating convection-working gases and liquid.
If heating moves molecules far enough apart, the critical temperature will be reached, at which point the influence of attractive forces is almost completely overcome. The molecules are no longer constrained. The molecules, now a gas, would be able to move about freely and completely fill the volume available within formation porosity. Gases are characterized by their sensitivity to changes in temperature and pressure. In the kinetic gas theory, gas pressure increases when a gas is enclosed in a fixed volume and its temperature is raised. The gas pressure is the measure of the average speed at which the gas molecules move about. SCFs form when the rate of a gas compression is high enough to saturate neighboring molecules without volume increases (a temporary energy potential stored). When the temperature is raised, the average speed of the particles increases, as does their energy. Nitrogen diamers SCFs strike the hydrocarbon formation walls at higher speed, saturating hydrocarbons with energy potential, and thus exert a larger force between the wall and hydrocarbons, migrating the hydrocarbons at greater distances faster. Reference to hydrocarbon-bearing formations may include any hydrocarbon formation and does not limit this invention to oil and gas recovery.
This invention teaches that convective currents can be added to any hydrocarbon formation by sealing the well hole with a plurality of seals that seal gas pressures down hole during heating, which will increase the pressure and penetration of working gas, “stripping” hydrocarbons from hydrocarbon-bearing formations. In this invention, gas compressors or supply lines can be inserted within the plurality of seals, forcing convection-working gases to cycle back to the heat source within the hydrocarbon formation, increasing distance penetration of working gases. Hydrocarbon-bearing formations have a wide range of pore sizes, which may require forced convection in situ cycled between the pluralities of down hole seals. This invention teaches that holding the gases within a natural or forced convection heat until the heavier organics are decomposed down hole can process all the organics and gases in the hydrocarbon formation, meeting environmental emission requirements. This is in-situ refining.
Fuel cell intake air is vacuumed, blown, or compressed mechanically to move atmospheric air through the fuel cell to deliver oxidants. This invention teaches that heating the working gas from hydrocarbon formations from fuel cell waste heat through a down hole heat exchanger provides all the fuel to produce electricity, steam, and nitrogen. Intake air is vacuumed against the oxygen adsorption site of a fuel cell, providing oxygen to the fuel cell. A very simple down hole in-situ fuel cell system would require an air blower or compressor at a parasitic loss because it would have to mechanically move atmospheric air through the fuel cell to deliver oxygen from air. The down hole heat exchanger on the fuel cell housing provides heat to decompose hydrocarbons for fuel gases, depending on the fuel cell type. Solid oxide is the preferred fuel cell type because it can react with a family of hydrocarbon sourced gases—a hybrid combination of different types of fuel cells can be applied to refine decomposed hydrocarbons. This invention teaches that an optional manifolding system and adsorbents species can be applied and customized to process difference ratios of organic species available across an infinitely variable range of formations. Any number of these heat exchanger bore hole sealed systems can be applied in the same bore hole, which is governed by the thickness and number of formations. Steam can be applied to damage and collapse an upper formation to increase the sealing of the lower formation. Collapsing formations, whether below, above, or around the bore hole, is a professional judgment of the geologist managing the hydrocarbon production. An air supply, fuel cell, and sealed heat exchanger plumbed with conduit to infuse nitrogen into the formation and release steam to atmosphere or infusion into a formation are all that is needed to make the system work.
The oxygen required for a fuel cell comes from air mechanically moved to the fuel cell. A reformer turns hydrocarbon or alcohol fuels into hydrogen, which is then fed to the fuel cell. Unfortunately, reformers are not perfect. They generate heat and produce other gases besides hydrogen. They use various devices to try to clean up the hydrogen, but even so, the hydrogen that comes out of them is not pure, and this lowers the efficiency of the fuel cell. Methanol is a liquid fuel that has properties to gasoline. It is just as easy to transport and distribute, so methanol may be a likely candidate to power fuel cells.
Five major types of fuel cells exist, and each has a different operating temperature, as follows: Fuel cells such as polymer electrolyte membrane fuel cells, 75° C. (180° F.); alkaline fuel cells, below 80° C.-75° C. (180° F.); phosphoric acid fuel cells, 210° C. (400° F.); molten carbonate fuel cells (MCFC) 650° C. (1200° F.); SOFCs, 800° C.-1000° C. (1500° F.-1800° F.). MCFCs and SOFCs have operating temperatures high enough to desorb and strip hydrocarbon bearing formations at 1200° F. to 1800° F.
MCFC uses a carbonate-salt-impregnated ceramic matrix as an electrolyte. Because MCFCs operate at 800° F., they are best suited to large, stationary applications. Yet they potentially have the most to gain, as they operate at 85 percent efficiency with cogeneration. They will be especially useful in hospitals, hotels, or other industrial applications that require electricity and heating (or cooling) around the clock.
SOFCs are best suited for large-scale stationary power generators that could provide electricity for factories or towns. SOFCs use a prefabricated ceramic sandwich between electrodes. Like MCFCs, they operate at higher temperatures (about 1000° F.) and make excellent co-generation devices for industrial applications where high temperature steam is required.    www.eere.energy.gov/hydrogenandfuelcells/fuelcells/types.html
One of the characteristics of an SOFC is that the fuel must be injected into the cell chamber at relatively high pressure of three to five atmospheres. When using gaseous fuels, this requirement for fuel compression requires significant power, which must be considered part of the system when calculating net power output. The fuel compressor is a parasitic load reducing fuel efficiency. Two examples: a Capstone® Turbine C30 generates 30 kW/hr and would require a minimum of 4.4 kW/hr fuel compressor, compared to model CapStone® Turbine C60, which generates 60 kW/hr and would require up to a 7.5 kW/hr fuel compressor.
Synthetic molecular sieves are porous, crystalline alumino-silicates that function much like a natural sieve; they adsorb some molecules and reject others. The absorption and desorption are completely reversible. Custom synthetic molecular sieves are applied in above ground modem oil refineries as molecular gas separator beds. In contrast, hydrocarbon-bearing formations are a natural composite of several natural molecular sieve species, which in a past natural environment have adsorbed a variety of organic hydrocarbons. In addition, the organic molecules physically imbedded in the natural hydrocarbon-bearing sieves have adsorbed gas molecules (e.g. hydrogen, methane, carbon dioxide). The molecular variety of organics in hydrocarbon-bearing formations is related directly to several natural molecular sieve species. Since molecular sieves adsorb materials through physical forces rather than through chemical reaction, they retain their original chemical state when the adsorbed molecular is desorbed. There are five types of adsorption/desorption cycles:    1. Thermal swing cycles involving rising desorption temperatures,    2. Pressure or vacuum swing cycles involving decreased desorption pressures,    3. Purge-gas stripping cycles using a non-adsorbed purge gas,    4. Displacement cycles using an adsorbable purge to displace the adsorbed material, and    5. Adsorptive heat recovery, using the retained heat of absorption to desorb certain molecules (e.g., water).
This invention teaches applying all five of the above-mentioned adsorption/desorption cycles to produce nitrogen compounds that react violently with hydrocarbons.
Yet a further drawback of the prior art is that the working gas required to recover hydrocarbons was not a combined non-reactive and reactive nitrogen compound. Stationary hydrocarbon-bearing formation requires working gas penetration radially from the bore hole into the depth of a hydrocarbon-bearing formation rather than the limits of conductive and radiant heat limited to the immediate proximity of the heat source. Hydrogen is released from the hydrocarbon-bearing formation when heated. This invention teaches methods of pressuring the hydrogen into the porous hydrocarbon-bearing formation, penetrating the hydrocarbon-bearing bed with a hot working gas at greater distances and variable pressures.
The alternative recovery process involves in-situ operations wherein bore holes drilled into subterranean hydrocarbon formations vertically, horizontally, and at angles are combined with various apparatus intended to recover oil and/or gas from the surrounding hydrocarbon-bearing formations.
To be considered economically feasible, a recovery system must be capable of functioning when applied to hydrocarbon-bearing formations located at any depth, even at the most minimum of depths such as when the overburden may extend only five feet in depth, thereby avoiding the necessity of drilling bore holes of extreme depths. Additionally, a viable system should integrate cogeneration systems that manage heat and should, once in place and operational, be capable of producing commercially acceptable electricity and water from the gas for an extended period of time.
In accordance with the present invention, the working fluid can be heated. Thermal chemical reaction will not occur, and catalytic reaction will be easier to manage, since the working gas physically moves from one location to the other by pressure and heat. Further, in some embodiments the working gas contains multiple gases: hydrogen, helium, propane, methane, and carbon dioxide.
Propane gas is affected by gravity, moving downward, and can be released into the drill hole to penetrate the hydrocarbon pores, providing a catalyst that can be added to start a chemical reaction within the bore hole and then substantially removed. Some catalytic reactions need an even distribution of catalyst, and this technology can provide an aggregate effect, gathering density, or a uniform effect. Prior art does not teach uniform gradient or thermal processing or reactive gas that compresses working gases into SCFs that saturate and then migrate hydrocarbons at any distance.